CN115184423A - Metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film and preparation method and application thereof - Google Patents
Metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a metal nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film, which comprises the steps of dissolving a nitrogen-sulfur-containing compound in a graphene oxide aqueous solution, drying to form a film, and then annealing at a high temperature to obtain an N and S co-doped film precursor; then dipping the mixture into a metal salt aqueous solution for carrying out a load reaction, and then washing and drying the mixture to obtain the catalyst. According to the method, firstly, a porous structure of a graphene film is constructed while nitrogen and sulfur are codoped, and then a simple impregnation method is adopted to realize uniform loading of metal nanoparticles on the surface of a graphene sheet layer and between the sheet layers through charge transfer between metal ions and heteroatoms and interaction between the metal ions and graphene oxide; the obtained graphene film has the characteristics of porous structure, flexibility, self-support, excellent electrocatalysis performance and the like; the method is suitable for the fields of electrocatalytic biosensing and the like; the related preparation method is simple, has low requirements on equipment, mild and controllable reaction conditions and low production cost, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a metal nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film, and a preparation method and application thereof.
Background
The graphene film has good conductivity, flexibility and mechanical strength, and can be directly used for preparing an unsupported light and thin flexible electrode without adding other electrode assemblies. However, the enzyme-free electrochemical sensing device constructed based on the unsupported graphene paper electrode and the application research thereof are still in the initial stage, and the sensitivity and the selectivity of the enzyme-free electrochemical sensing device are still to be further improved.
Generally, graphene paper can be used as a substrate, various metal or alloy nanoparticles are loaded on the graphene composite paper, and the graphene composite paper is used as an unsupported flexible electrode to construct an electrochemical biosensor. However, since the active sites exist only on the surface of the graphene paper substrate, the graphene paper substrate has no active sites inside, which limits the full utilization of the internal structure of the carrier. Secondly, active metals can be loaded on the surface and the interior of the graphene paper substrate so as to increase electrocatalytic active sites; such composite paper is typically formed by stacking graphene nanoplates in layers under pi-pi action [ Saha, b.; baek, s.; lee, J.high throughput sensitive and foldable paper sensors based on reduced graphene oxide. ACS appl. Mater. Interfaces 2017,9,4658-4666 ], which has compact structural hierarchy and poor mass transfer effect; and the electrolyte is difficult to diffuse into the composite paper to contact with the supported active metal, so that the catalytic contribution of the internal active sites is limited. In addition, the graphene carrier has no catalytic activity and weak interaction with loaded metals, so that the activity and stability of the graphene composite paper biosensor are restricted. In general, the activity of supported catalysts is closely related to the number of their exposed active sites, the micro-nano structure and the synergy between the components [ Liu, j.; bo, x.j.; zhao, z.; guo, L.P.high hly expanded Pt nanoparticles supported on a porous graphene for electrochemical detection of a hydrogen peroxide in living cells.biosens.Bioelectron.2015,74,71-77 ]. The conventional supported graphene paper electrode has certain limitations in the aspects of electrode structure and performance, and the full play of the performance of the graphene composite paper electrode material is limited. Further exploring a simple and efficient preparation method of the graphene film, and having important research and application values.
Disclosure of Invention
The invention mainly aims to solve the problems and the defects in the prior art, and provides a metal nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film, which is characterized in that firstly, a porous structure of the graphene film is constructed while nitrogen-sulfur co-doping is carried out, and then a simple impregnation method is adopted, so that the uniform loading of metal nanoparticles on the surface of a graphene sheet layer and between sheet layers is realized through charge transfer between metal ions and heteroatoms and interaction between the metal ions and graphene oxide; the obtained graphene film has the characteristics of porous structure, flexibility, self-support, excellent electrocatalytic performance and the like; the method is suitable for the fields of electrocatalysis biosensing and the like; the related preparation method is simple, has low requirements on equipment, mild and controllable reaction conditions and low production cost, and is suitable for popularization and application.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film comprises the following steps:
1) Dissolving a nitrogen-sulfur-containing compound in a graphene oxide aqueous solution, uniformly mixing and stirring until the nitrogen-sulfur-containing compound is completely dissolved, drying to form a film, then performing high-temperature annealing, and performing further annealing to complete the doping of two kinds of heteroatoms to obtain an N-S co-doped film precursor;
2) And soaking the obtained N and S co-doped film precursor in a metal salt aqueous solution, carrying out a loading reaction, and then washing and drying to obtain the nitrogen and sulfur co-doped porous graphene film loaded with the metal nanoparticles.
In the scheme, the concentration of the graphene oxide aqueous solution is 3-10mg/mL.
In the above scheme, the nitrogen-sulfur-containing compound is at least one of thiourea, ammonium thiocyanate and the like; the mass ratio of the graphene to the graphene is (0.5-5): 1.
Preferably, the drying and film forming step adopts a freeze drying method, the temperature is-60 to-48 ℃, the vacuum degree is 7 to 25Pa, and the time is 8 to 12 hours. Under the vacuum freeze-drying condition, moisture directly sublimates, has fully guaranteed that the lamellar structure of film can not pile up, and low temperature has also guaranteed simultaneously that graphene oxide can not be reduced at dry in-process. Traditional oven drying and natural air-drying can not avoid the problem that the lamella piles up, and oven drying can make the reduction of being heated of oxidation graphite alkene.
In the scheme, the high-temperature annealing temperature is 380-1000 ℃, and the time is 2-6h.
In the above scheme, the metal salt is selected from one or more of iron salt, nickel salt, cobalt salt, copper salt, palladium salt, gold salt, platinum salt, silver salt, and the like.
Further, the ferric salt can be one or more of ferric chloride, ferric nitrate and the like; the nickel salt can be one or more of nickel chloride, nickel nitrate and the like; the cobalt salt can be one or more of cobalt chloride, cobalt nitrate, etc.; the copper salt can be one or more of copper chloride, copper nitrate and the like; the palladium salt can be one or more of potassium chloropalladate, potassium chloropalladite and the like, and the gold salt can be potassium chloropalladite and the like; the platinum salt can be potassium chloroplatinate, etc.; silver nitrate can be used as the silver salt.
In the scheme, the mass ratio of the N and S co-doped film precursor introduced in the step 2) to the metal element introduced by the metal salt is 1 (0.005-0.1).
Preferably, when the metal salt is palladium salt, the mass ratio of the introduced N and S co-doped film precursor to the metal element introduced by the metal salt is 1 (0.005-0.05).
In the scheme, the load reaction adopts a light-proof ice-bath condition to ensure that the nano particles are not reduced under the influence of illumination and temperature; the loading time is 4-10h.
According to the metal nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film prepared by the scheme, nitrogen exists in a graphene structure in the form of graphite nitrogen, pyridine nitrogen and pyrrole nitrogen, sulfur exists in the form of thiophene sulfur, and metal particles exist on the surface of graphene lamellar layers and among the lamellar layers in the form of extremely fine nanoparticles (1-10 nm); the obtained film has a uniform fold and micron-sized pore structure; the content of metal element is 0.5-5wt.%.
The metal nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film obtained by the scheme is used as a self-supporting electrode and is applied to the fields of electrochemical biosensing and the like; the method is particularly suitable for constructing an enzyme-free electrochemical sensing device.
The method adopts new strategies of 'inert matrix doping synergy', 'high-density nano metal loading' and 'porous mass transfer structure construction', so that active sites on the surface and inside of the graphene substrate are fully exposed, and metal nanoparticles are uniformly loaded on the surface of the graphene sheet layer and between the graphene sheet layers; the method has the advantages that the regulation and control of the performance of the graphene film catalytic electrode and the construction of a sensitization electrode interface are realized, multi-level combination of a (doped) graphene porous skeleton structure and metal nanoparticles can be realized, the excellent electrical, chemical and mechanical properties of graphene can be fully exerted, the electrocatalytic activity of the graphene is comprehensively improved by utilizing the synergistic effect among the components, the limitation of the conventional electrode structure can be effectively broken through, and the electrochemical sensing performance is improved.
The method can provide a key technology for preparing a novel unsupported flexible graphene-based porous composite paper electrode material, and has a certain promotion effect on the development of a high-sensitivity enzyme-free electrochemical biosensor and the like.
Compared with the prior art, the invention has the following beneficial effects:
1) The preparation process is simple, no additional reducing agent is required to be introduced into the whole process, and the production efficiency is high; the related reaction conditions are mild and controllable, complex reaction equipment is not needed, the implementation is easy, and the application prospect is good;
2) According to the preparation method, thiourea and the like are introduced to serve as a pore-forming agent and a nitrogen-sulfur source in the preparation process of the graphene oxide film, so that high efficiency and co-doping of heteroatoms such as nitrogen and sulfur and construction of a porous structure of the graphene film can be synchronously realized, uniform loading of subsequent metal nanoparticles is facilitated, and the electrocatalytic activity of the obtained composite material is remarkably improved; the related operation is simple and convenient, the cost is lower, and the method is suitable for popularization and application;
3) The prepared metal nanoparticle-loaded nitrogen-sulfur-codoped porous graphene material has the characteristics of ultra-large specific surface area, excellent catalytic performance and the like, and can be applied to the fields of electrocatalysis, organic catalysis, biosensing and the like.
Drawings
Fig. 1 is a morphology diagram of a Pd-nanoparticle-supported nitrogen-sulfur-codoped porous graphene film obtained in example 1 of the present invention; the graph a is an unfolded shape, and b and c are shapes under different folding conditions;
fig. 2 is a scanning electron microscope image of the Pd nanoparticle-supported nitrogen and sulfur co-doped porous graphene thin film obtained in example 1 of the present invention (fig. a and c are front surfaces of the thin film, fig. b is a back surface of the thin film, and d is a cross section);
fig. 3 is a transmission electron microscope image of the surface and the cross section of the Pd nanoparticle-supported nitrogen and sulfur co-doped porous graphene thin film obtained in example 1 of the present invention;
fig. 4 is a Raman spectrum of the Pd-supported nanoparticle nitrogen and sulfur co-doped porous graphene film obtained in example 1 of the present invention;
fig. 5 is an XRD test chart of the Pd-supported nanoparticle nitrogen and sulfur co-doped porous graphene film obtained in example 1 of the present invention;
fig. 6 is an XPS spectrum of the Pd-supported nanoparticle nitrogen and sulfur co-doped porous graphene film obtained in example 1 of the present invention;
fig. 7 is an EDS elemental surface scanning view of the Pd nanoparticle-supported nitrogen-sulfur co-doped porous graphene thin film obtained in example 1 of the present invention;
fig. 8 shows the electrocatalytic performance test results of the Pd-nanoparticle-supported nitrogen and sulfur co-doped porous graphene film obtained in example 1 of the present invention on hydrogen peroxide with different concentrations;
fig. 9 is an electrocatalytic performance test result of the Pd nanoparticle-supported porous graphene thin film obtained in comparative example 1;
fig. 10 is a scanning electron microscope image of the Pd nanoparticle-supported porous graphene film obtained in comparative example 2;
fig. 11 shows the electrocatalytic performance test result of the Pd nanoparticle-supported porous graphene thin film obtained in comparative example 2 on hydrogen peroxide.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows.
In the following examples, graphene oxide used was prepared from graphite powder (purchased from Qingdao Huatai lubrication sealing science and technology Co., ltd.), concentrated sulfuric acid, sodium nitrate and potassium permanganate by a modified Hummers method; the preparation method comprises the following steps: adding 2.00g of graphite powder, 1.00g of sodium nitrate and 69mL of concentrated sulfuric acid (98%) into a 500mL three-neck flask, uniformly mixing under the conditions of ice bath and mechanical stirring, and weighing 6.00g of KMnO 4 Grinding and crushing in a mortar, slowly adding into a three-neck flask, controlling the temperature in the adding process to be about 5 ℃, and stirring for 2 hours under ice bath conditions after the adding is finished; then heating to 35 ℃, stirring for reacting for 2 hours, slowly dropwise adding 90mL of distilled water into a three-neck flask, heating to 95 ℃ after dropwise adding is finished, keeping the temperature, and stirring for 0.5 hour; slowly adding 280mL of distilled water dropwise into the obtained reaction solution, keeping the temperature for reaction for 5min, stopping heating, cooling the reaction solution to room temperature, and slowly adding 4.0mL of H dropwise into the reaction solution 2 O 2 (30%); standing for layering, removing supernatant, washing the lower layer solid with hydrochloric acid (3.3%) and distilled water in sequence, washing to near neutrality to obtain GO dispersion, and bottling. (GO concentration can be obtained by lyophilization means).
In the following embodiments, the method for testing the electrochemical performance of the nitrogen-sulfur co-doped porous graphene film includes the following steps: at the ambient temperature (25 ℃) in the laboratory, KH with the pH value of 7.4 is firstly prepared 2 PO 4 -K 2 HPO 4 Buffer System (PBS) and 1M H 2 O 2 Controlling the area of the working electrode below the liquid level to be 0.6cm multiplied by 1cm; performing cyclic voltammetry and current-time testing by using a three-electrode system (an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and a cut nitrogen-sulfur co-doped porous graphene film is used as a working electrode) to obtain a cyclic voltammetry curve and a current-time curve, calculating to obtain a standard curve and an equation cyclic voltammetry testing voltage of-0.8-0.8V, and performing at a sweep rate of 50 mV/s; each time H is added 2 O 2 After the solution, H was calculated and recorded 2 O 2 Gradient concentration of (2), starting magnetic stirring toAnd uniformly mixing the liquid, stopping stirring after the liquid is completely mixed, and performing cyclic voltammetry.
Example 1
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is prepared by the following specific steps:
1) Taking 25mL of graphene oxide aqueous solution with the concentration of 4mg/mL, adding 100mg of solid thiourea (feeding the graphene oxide and the nitrogen-sulfur compound according to the mass ratio of 1;
2) Dissolving 0.0117g of potassium chloropalladite solid in 100mL of ice water, adding the obtained N and S co-doped film precursor into the ice water solution (the mass ratio of the introduced palladium element of the N and S co-doped film precursor to the potassium chloropalladite solid is 1.02), carrying out light-shading ice bath for 6h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), thereby obtaining the Pd nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film.
The product obtained in this example was tested for metal content of 1.8wt.% by inductively coupled plasma mass spectrometry (ICP-MS).
FIG. 1 is a diagram showing the morphology of the product obtained in this example, and the obtained film has better mechanical properties (flexible, foldable, and cuttable).
Fig. 2 is an SEM image of the product obtained in this example, and it can be seen that the prepared thin film catalyst is in a lamellar fold structure, has a rich porous structure, and has uniform pore distribution and wide pore size distribution.
FIG. 3 is a HAADF-STEM test chart of the product obtained in this example, and it can be seen that the metal exhibits very fine nanoparticles of about 1-5 nm.
FIG. 4 is a Raman spectrum of the product obtained in this example, I D /I G The comparison shows that the incorporation of thiourea increases the defect level of the thin film catalyst.
FIG. 5 is an XRD spectrum of the product obtained in this example, and it can be seen that a diffraction peak corresponding to the [002] crystal plane of graphitic carbon is observed at around 26 ℃ and a diffraction peak corresponding to the [100] crystal plane of graphitic carbon is observed at around 43 ℃.
Fig. 6 is an XPS spectrum of the product obtained in this example, and the results show that the product is mainly composed of C, N, O, S and Pd elements, the atomic contents of nitrogen and sulfur are 6.75% and 0.67%, respectively, and the specific existence forms of different elements in the material can be known.
Fig. 7 is a scanning chart of EDS elements of the product obtained in this example, and it can be seen that C, N, S, and Pd are uniformly dispersed in the composite system, further proving uniform doping of nitrogen and sulfur and uniform loading of Pd nanoparticles.
FIG. 8 shows the results of Cyclic Voltammetry (CV) for electrochemical sensing test, which is performed on the working electrode prepared by cutting and controlling the area of the product obtained in this example, so that the immersed area of the electrode is kept unchanged, and the results show that the prepared material has good response to hydrogen peroxide and is detected within 8mM when being used as an electrochemical biosensing electrode.
Example 2
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is prepared by the following specific steps:
1) Taking 25mL of graphene oxide aqueous solution with the concentration of 6mg/mL, adding 75mg of solid thiourea (feeding the graphene oxide and the nitrogen-sulfur compound according to the mass ratio of 2;
2) Dissolving 0.0274g of potassium chloropalladite solid in 100mL of ice water, adding the obtained N and S co-doped film precursor into the ice water solution (the mass ratio of the N and S co-doped film precursor to palladium introduced by the potassium chloropalladite solid is 1.05), carrying in a light-shielding ice bath for 4h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), thereby obtaining the Pd nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film.
Example 3
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is specifically prepared by the following steps:
1) Taking 15mL of graphene oxide aqueous solution with the concentration of 5mg/mL, adding 150mg of solid thiourea (the mass ratio of the graphene oxide to the nitrogen-sulfur-containing compound is 1;
2) Dissolving 0.0060g of potassium chloropalladite solid in 100mL of ice water, adding the obtained N and S co-doped film precursor into the ice water solution (the mass ratio of the N and S co-doped film precursor to palladium element introduced by the potassium chloropalladite solid is 1.01), carrying in a light-shielding ice bath for 5h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), thereby obtaining the Pd nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film.
Example 4
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is prepared by the following specific steps:
1) Taking 30mL of graphene oxide aqueous solution with the concentration of 6mg/mL, adding 540mg of solid thiourea (the mass ratio of the graphene oxide to the nitrogen-sulfur-containing compound is 1;
2 (0.0186 g of cobalt chloride solid is dissolved in 100mL of ice water, the obtained N and S co-doped film precursor is added into the ice water solution (the mass ratio of the N and S co-doped film precursor to the cobalt chloride solid introduced cobalt element is 1.05), the film is loaded in a light-shielding ice bath for 10 hours, the film is taken out, the film is washed by deionized water for multiple times, and the film is freeze-dried to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), so that the Pd nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film is obtained.
Example 5
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is prepared by the following specific steps:
1) Taking 25mL of 3mg/mL graphene oxide aqueous solution, adding 300mg solid thiourea (feeding the graphene oxide and the nitrogen-sulfur-containing compound according to a mass ratio of 1;
2) Dissolving 0.0027g of potassium chloroplatinite solid in 100mL of ice water, adding the obtained N and S co-doped film precursor into the ice water solution (the mass ratio of platinum elements introduced into the N and S co-doped film precursor and the potassium chloroplatinite solid is 1.005), carrying out light-shading ice bath for 4h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), thus obtaining the Pt nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film.
Example 6
A loaded metal nanoparticle nitrogen and sulfur co-doped porous graphene film is prepared by the following specific steps:
1) Taking 35mL of graphene oxide aqueous solution with the concentration of 5mg/mL, adding 700mg of solid thiourea (the mass ratio of the graphene oxide to the nitrogen-sulfur-containing compound is 1;
2) Dissolving 0.0003g of ferric nitrate solid in 100mL of ice water, adding the obtained N and S co-doped film precursor into the ice water solution (the mass ratio of the N and S co-doped film precursor to iron in the ferric nitrate is 1.0005), carrying out light-shielding ice bath loading for 10 hours, taking out, washing with deionized water for multiple times, and carrying out freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, and the surface diameter is 50 mm), thereby obtaining the Fe nanoparticle-loaded nitrogen-sulfur co-doped porous graphene film.
Comparative example 1
A metal nanoparticle loaded graphene film is specifically prepared by the following steps:
1) Taking 25mL of 4mg/mL graphene oxide aqueous solution, after film making, directly freeze-drying to form a film (-50 ℃,20 Pa), then annealing under the same conditions (high-temperature annealing for 2h at 700 ℃), cooling to room temperature, and weighing to obtain 0.1809g precursor film;
2) Accurately weighing 0.011g of potassium chloropalladite solid with the theoretical loading of palladium nanoparticles of 2 percent, dissolving the potassium chloropalladite solid in 100mL of ice water, adding the precursor film into the ice water solution (the mass ratio of the precursor film to the potassium chloropalladite solid is 1.02), carrying out shading ice bath loading for 6h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film (the volume of the liquid film before freeze-drying is 2.5mL, the surface diameter is 50 mm), thus obtaining the porous graphene film loaded with the Pd nanoparticles.
Through tests, the precursor has good mechanical properties, and is prepared into a working electrode for performing Cyclic Voltammetry (CV) of electrochemical sensing, and test results show that the material can hardly be detected by 1mM hydrogen peroxide solution, and specific test results are shown in FIG. 9.
Comparative example 2
A preparation method of a metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film comprises the following steps:
1) Taking 25mL of graphene oxide aqueous solution with the concentration of 4mg/mL, directly freeze-drying to form a film after the film is prepared, and weighing 0.0903g of the film; cutting the film into strips, uniformly spreading thiourea with the mass ratio of 1 on the surface of the film, annealing at the same condition (700 ℃) for 2h at high temperature, cooling to room temperature, and weighing to obtain 0.1657g of a precursor film;
2) Accurately weighing 0.0102g of potassium chloropalladite solid with the theoretical loading of the palladium nanoparticles being 2% to dissolve in 100mL of ice water, adding the precursor film into the ice water solution (the mass ratio of the precursor film to the potassium chloropalladite solid is 1.02), carrying out light-shielding ice bath loading for 6h, taking out, washing with deionized water for multiple times, and freeze-drying to form a film to obtain the porous graphene film loaded with the Pd nanoparticles.
The structure of the composite material obtained in the comparative example is characterized, and a scanning electron micrograph is shown in figure 10, so that the product obtained by firstly preparing the graphite oxide film and then compounding the graphite oxide film with thiourea can not obtain a porous structure. In addition, the graphene sheet layer stacked structure is not beneficial to doping of inner layer graphene (XPS analysis results of inner layer materials after the outer layer of the composite film is stripped show that the atomic contents of nitrogen and sulfur are 0.86% and 0.12%, respectively), and the inner material of the film cannot load active metal to be in contact with electrolyte, so that no catalytic contribution is generated inside the film catalytic material.
The cyclic voltammetry test was performed on the product obtained in this example according to the above method, and the result is shown in fig. 11, from which, it can be seen that the product obtained in this example has a small response signal to hydrogen peroxide, which is much smaller than the signal value of the product obtained in example 1.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (9)
1. A preparation method of a metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film is characterized by comprising the following steps:
1) Dissolving a nitrogen-sulfur-containing compound in a graphene oxide aqueous solution, uniformly mixing and stirring until the nitrogen-sulfur-containing compound is completely dissolved, and performing high-temperature annealing after drying and film forming to obtain an N-S co-doped film precursor;
2) And soaking the obtained N and S co-doped film precursor into a metal salt aqueous solution, carrying out a load reaction, and then washing and drying to obtain the metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film.
2. The method according to claim 1, wherein the concentration of the aqueous graphene oxide solution is 3 to 10mg/mL.
3. The preparation method according to claim 1, wherein the nitrogen-sulfur compound is at least one of thiourea and ammonium thiocyanate; the mass ratio of the graphene to the graphene is (0.5-5): 1.
4. The method according to claim 1, wherein the high temperature annealing is performed at 380-1000 ℃ for 2-6h.
5. The method according to claim 1, wherein the metal salt is selected from one or more of iron salt, nickel salt, cobalt salt, copper salt, palladium salt, gold salt, platinum salt and silver salt.
6. The production method according to claim 1, wherein the mass ratio of the N, S co-doped film precursor introduced in step 2 to the metal element introduced by the metal salt is 1 (0.005-0.1).
7. The preparation method according to claim 1, wherein the loading reaction adopts a light-shielding ice-bath condition, and the loading time is 4-10h.
8. The nitrogen and sulfur co-doped porous graphene film prepared by the preparation method of any one of claims 1 to 7.
9. The metal nanoparticle-loaded nitrogen and sulfur co-doped porous graphene film of claim 8 is used as a self-supporting electrode and applied to electrochemical biosensing.
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